The present invention relates to musk aroma-imparting, augmenting and enhancing mixtures of oxomacrocyclic compounds containing greater than about 40 weight % xcex943-cyclotetradecen-1-one and greater than about 40 weight % cyclo-tetradecanone and less than about 5 weight % xcex942-cyclotetradecen-1-one and a process for preparing such mixtures by means of a chemo-selective catalytic hydrogen of mixtures containing greater than 15% by weight of the xcex942-cyclotetradecen-1-one and greater than 45% by weight of the xcex943-cyclotetradecen-1-one.
There has been considerable work performed relating to substances which can be used to impart, alter, modify or enhance fragrances to or in various consumable materials. These substances are used to diminish the use of natural materials particularly in the musk aroma area where the use of natural materials is being replaced by the use of synthetic materials which provide more uniform and predictable properties in the finished product. Strong, substantive, sweet, warm, natural xe2x80x9canimal-muskxe2x80x9d aromas with an absence of oily and waxy nuances in the topnotes, middle notes and undertones, heretofore have been highly sought after by those skilled in the perfumery arts.
Thus, prior art xe2x80x9canimal-muskxe2x80x9d aroma-imparting, augmenting and enhancing mixtures containing significant concentrations of cyclotetradecanone, xcex942-cyclo-tetradecen-1-one and xcex943-cyclotetradecen-1-one, for example, those disclosed in U.S. Pat. No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated herein by reference, and those disclosed by Stork and Macdonald at pages 1264 and 1265 of the Journal of the American Chemical Society, Volume 97, No.5, Mar. 5, 1975 which have desirable musk aromas all have the undesirable oily and waxy nuances present in their topnotes, middle notes and undertones, and impart these nuances to finished products produced therefrom.
Thus, nothing in the prior art discloses or suggests cyclotetradecanone/mono-unsaturated cyclotetradecen-1-one mixtures which have desirable natural xe2x80x9canimal-muskxe2x80x9d aromas but which have no oily and waxy nuances present in the topnotes, middle notes or undertones thereof. We have now discovered that the direct cause of the presence of such waxy and oily notes is the presence in the aroma-imparting, augmenting and enhancing mixture of significant concentrations, greater than 15 weight % on a solvent-free basis, of the isomer, xcex942-cyclotetradecen-1-one; but if the concentration, on a solvent-free basis, were to be reduced to less than 5 weight % of the mixture, the existence of the oily and waxy nuances becomes imperceptible.
Accordingly, there exists a need for a practical method to produce cyclotetradecanone/xcex943-mono-unsaturated cyclotetradecen-1-one mixtures which have the aforementioned desirable aroma properties but which have insignificant concentrations, less than 5 weight % on a solvent-free basis, of xcex942-cyclotetradecen-1-one.
Our invention is directed to strong, substantive, sweet, warm, natural xe2x80x9canimal-muskxe2x80x9d aroma-imparting, augmenting and enhancing macrocyclic musk compositions which are mixtures consisting essentially of oxocarbocyclic compounds containing greater than about 40 weight % xcex943-cyclotetradecen-1-one and greater than about 40 weight % cyclotetradecanone, less than 5 weight %, of xcex942-cyclotetradecen-1-one.
More specifically, our invention is directed to macrocyclic musk compositions of matter consisting essentially of:
(a) from about 40 up to about 60 weight %, on a solvent-free basis, of cyclotetradecanone;
(b) from about 40 up to about 60 weight %, on a solvent-free basis, of xcex943-cyclotetradecen-1-one; and
(c) less than 5 weight %, on a solvent-free basis, of xcex942-cyclotetradecen-1-one, the weight ratio of cyclotetradecanone: xcex943-cyclotetradecen-1-one being from about 6:4 down to about 4:6.
A preferred composition of our invention consists essentially of:
(a) about 50% by weight, on a solvent-free basis, of cyclotetradecanone;
(b) about 45% by weight, on a solvent-free basis, of xcex943-cyclotetradecen-1-one; and
(c) less than 5 weight %, on a solvent-free basis, of xcex942-cyclotetradecen-1-one.
The process of our invention for producing the macrocyclic musk compositions of our invention comprises the steps of:
(a) admixing a cyclotetradecenone reactant mixture comprising greater than 45% by weight of xcex943-cyclotetradecen-1-one and greater than 15% by weight of xcex942-cyclotetradecen-1-one with a hydrogenation reaction solvent to form a solvent-reactant mixture, with the weight ratio of solvent:cyclotetradecenone reactant mixture being from 20:70 up to 70:20;
(b) treating the resulting solvent-reactant mixture with hydrogen in the presence of a chemo-selective hydrogenation catalyst in a concentration of from about 0.1% up to about 0.5% by weight of the reaction mixture, at a temperature in the range of from about 15xc2x0 C. up to about 35xc2x0 C. and at a pressure of from about 0 psig up to about 100 psig thus forming a hydrogenated product reaction mass, whereby a composition comprising, on a solvent-free basis, greater than about 40% by weight of cyclotetradecanone, greater than about 40% by weight of xcex943-cyclotetradecen-1-one and less than about 5% by weight of xcex942-cyclotetradecen-1-one is produced; and
(c) recovering the resulting macrocyclic musk composition from the hydrogenated product reaction mass (preferably by means of vacuum distillation).
Several techniques for the preparation of the cyclotetradecenone reactant mixtures may be used in the practice of our invention, for example:
(a) The process described in Example I at columns 11-14 of U.S. Pat. No. 4,183,965 issued on Jan. 15, 1980, the disclosure of which is incorporated herein by reference, or
(b) A process, as more particularly described herein in detail in Example I, infra, comprising the steps of (i) treating 3-hydroxycyclotetradecan-1-one in the vapor phase with a dehydrating quantity and concentration of anhydrous aluminum oxide particles, preferably from about 4 mesh up to about 8 mesh, at a dehydrating temperature, preferably from about 360xc2x0 C. up to about 400xc2x0 C., and pressure, preferably from about 1 mm Hg up to about 20 mm Hg, to form a dehydration product reaction mass and then (ii) recovering the cyclotetradecenone reactant mixture from the dehydration product reaction mass, preferably by means of vacuum distillation.
Preferably, the chemo-selective hydrogenation catalyst is a supported palladium catalyst containing from about 2 weight % palladium up to about 10 weight % palladium such as palladium on carbon, palladium on calcium carbonate and palladium on barium sulfate.
The hydrogenation reaction solvent is non-reactive with any reactant or reaction product, and is preferably methanol, ethanol, 2-propanol, 1-propanol, acetone, methylethylketone, methylisobutylketone, tetrahydrofuran or mixtures thereof.
A preferred set of hydrogenation reaction conditions is specifically set forth herein in Example II, infra.
Also, a preferred set of hydrogenation reaction conditions is as follows:
(i) Chemo-selective hydrogen catalyst: 5 weight % palladium on carbon;
(ii) Solvent: 2-propanol;
(iii) Hydrogenation reaction pressure: 100 psig;
(iv) Hydrogenation reaction temperature: 35xc2x0 C.
(v) Weight ratio of solvent:reactant mixture: 50:50.
In carrying out the hydrogenation reaction of our invention, treatment of the solvent-reactant mixture with hydrogen causes the percentage P of xcex942-cyclotetradecen-1-one in the composition to be reduced over the period of time, xcex8 (minutes) during which the hydrogenation takes place, according to either of the algorithms:
P=A(exp)(xe2x88x92xcex8K/xcex1)+Bxe2x80x83xe2x80x83(1) 
or
xcex8={xcex1ln A(Pxe2x88x92B)xe2x88x921}1/Kxe2x80x83xe2x80x83(2) 
wherein xcex8 represents the time in minutes as measured from the commencement of the hydrogenation reaction; and xcex1, A, B and K represent constants; and wherein:
xe2x80x83Pxe2x89xa70
xcex8xe2x89xa70;
15xe2x89xa6Axe2x89xa630;
0xe2x89xa6Bxe2x89xa65;
2.8xe2x89xa6Kxe2x89xa64.0; and
2xc3x97103xe2x89xa6xcex1xe2x89xa640xc3x97103.
In addition, the rate of change with respect to time of the percentage of xcex942-cyclo-tetradecen-1-one, dP/dxcex8, in the reactant-solvent mixture being hydrogenated is according to the algorithm:
dP/dxcex8=xe2x88x92AKxcex8Kxe2x88x921xcex1xe2x88x921(exp)(xe2x88x92xcex8Kxcex1xe2x88x921). 
The macrocyclic musk compositions of our invention and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, nitrites, esters, cyclic esters, ketones other than the ingredients of the macrocyclic musk compositions of our invention, hydrocarbons and natural essential oils may be admixed so that the combined odors of the individual components produce a pleasant and desired fragrance particularly and preferably in musk and xe2x80x9canimal-likexe2x80x9d fragrances. Such perfume compositions usually contain (a) the main note or the xe2x80x9cbouquetxe2x80x9d or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which are usually low boiling fresh smelling materials.
In the perfume composition, it is each of the individual components which contribute to its particular olfactory characteristics, but the over-all effect of the perfume composition will be the sum of the effects of each of the ingredients. Thus, the macrocyclic musk compositions of our invention can be used to alter the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by at least one other ingredient in the composition.
The amount of macrocyclic musk composition of our invention which will be effective in perfume compositions depends on many factors including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of the macrocyclic musk compositions of our invention and even less (e.g., 0.005%) can be used to impart sweet, warm, natural, xe2x80x9canimal muskxe2x80x9d aroma nuances (without oily and waxy notes) to soaps, anionic, cationic, nonionic and zwitterionic detergents, fabric softener articles, fabric softener compositions, hair preparations, cosmetics and other products. The amount employed can range up to 10% of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
The macrocyclic musk compositions of our invention are useful, taken alone or in perfume compositions as olfactory components in anionic, cationic, nonionic and zwitterionic detergents, soaps, fabric softener compositions, fabric softener articles for use in clothes dryers (e.g., BOUNCE(copyright), Procter and Gamble Company of Cincinnati, Ohio, U.S.A.), space odorants and deodorants, perfumes, colognes, toilet water, bath preparations such as bath oils and bath solids; hair preparations such as lacquers, brilliantines; creams; deodorants; hand lotions; sun screens; powders such as talcs, dusting powders, face powders and the like. When used as an olfactory component in perfume compositions or perfumed articles, such as anionic, cationic, nonionic and zwitterionic detergents, and in fabric softener compositions and fabric softener articles (e.g. for use in clothing dryers) as little as 0.05% of the macrocyclic musk compositions of our invention will suffice to impart a sweet, warm, natural xe2x80x9canimal-muskxe2x80x9d aroma, without the undesireable oily and waxy nuances. Generally no more than 5% of the macrocyclic musk composition of our invention is required in the perfume composition or in the perfumed article.
In addition, the perfume composition or fragrance composition of our invention can contain a vehicle or carrier for the macrocyclic musk compositions of our invention. The vehicle can be a liquid such as a non-toxic alcohol (e.g., ethanol) a non-toxic glycol (e.g., propylene glycol) or the like. The carrier can also be an absorbent solid, such as a gum (e.g., gum arabic, or xanthan gum) or components for encapsulating the composition (such as gelatin) as by means of coacervation. The carrier can be a microporous polymer for use in conjunction with particulate microporous polymer delivery systems, as disclosed in U.S. Pat. No. 6,213,409 issued on Apr. 10, 2001, the disclosure of which is incorporated herein by reference, or for use in conjunction with fiber delivery systems, as disclosed in U.S. Pat. No. 6,207,274 issued on Mar. 27, 2001, the disclosure of which is incorporated herein by reference.
It will thus be apparent that the macrocyclic musk compositions of our invention can be utilized to alter the sensory properties of a wide variety of consumable materials.
The following examples are illustrative and the invention is to be restricted thereto only as indicated in the appended claims. All parts and percentages given herein are by weight unless otherwise specified.